Color silver halide photographic materials containing bis-pyrazolone color couplers

ABSTRACT

A SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CAPABLE OF PROVIDING STABLE MAGENTA IMAGES CONTAINING A BIS-3UREIDO-5- PYRAZOLONE PREPARED BY THE REACTION OF A 3UREIDO-5-PYRAZOLONE WITH A COMPOUND HAVING AN ALDEHYDE GROUP.

3,834,908 COLOR SILVER HALIDE PHOTOGRAPHIC MATE- RIALS CONTAININGBIS-PYRAZOLONE COLOR COUPLERS Hiroshi Hara, Yukio Yokota, HiroyukiAmano, and Tokio Nishimura, Kanagawa, Japan, assignors to Fuji PhotoFilm Co., Ltd., Kanagawa, Japan N Drawing. Filed July 10, 1973, Ser. No.377,991 Claims priority, application Japan, July 11, 1972, 47/69,409Int. Cl. G03c 1/40 US. Cl. 96-100 2 Claims ABSTRACT OF THE DISCLOSURE Asilver halide color photographic material capable of providing stablemagenta images containing a bis-3- ureido-S- pyrazolone prepared by thereaction of a 3- ureido-S-pyrazolone with a compound having an aldehydegroup. 1

BACKGROUND OF THE INVENTION Field of the (Invention The presentinvention relates to a color photographic material, in particular, to asilver halide color photographic material containing a color couplerproviding particularly stable magenta dye images.

DESCRIPTION OF THE PRIOR ART It is well known in color photography thatcyan, magenta and yellow dye images are formed by the coupling reactionof the oxidation product of an aromatic primary amino developing agentand color forming couplers. Various kinds of pyrazolone derivatives arealso known as couplers for forming magenta color images.

However, magenta color images formed from known pyrazolone derivativesare generally unstable to heat and humidity and when the images areexposed to heat and moisture or stored for a long period of time, thelow density portions tend to fade.

This fading phenomenon is caused by unreacted couplers, and thistendency is particularly remarkable at low density portions containing alarge proportion of unreacted couplers [see P.W. Vittum; Journal ofAmerican Chemical Society, Vol. 72, l533(1950)].

Various methods of preventing the occurence of such fading of magentacolor images have been proposed. One is described in US. Pat. 3,140,177,wherein a color photographic material is treated by an acid processingsolution containing formalin in the final processing step of the colorphotographic material. However, this method is undesirable sinceformalin gives oif a bad smell and is toxic, and hence there is a dangerto humans during processing or from the waste solutions generated bysuch a processing. Another method is described in US. Pat. 3,468,666,wherein the bispyrazolone prepared by the condensation of3-acylamino-5-pyrazolone with an aldehyde is used as the magentacoupler. However, this latter method has the faults that thebispyrazolones do not give sufiicient color density upon colordevelopment and the color images formed therefrom are not fast to heatand moisture.

SUMMARY OF THE INVENTION One object of this invention is to provide acolor photographic material forming a fast or stable magenta color 1mae.

If has now been discovered that the above object of this invention canbe attained by using a bis-3-ureido-5- pyrazolone prepared by thereaction of a 3-ureido-5-pyrazolone with a compound having an aldehydegroup.

United States Patent O ice That is, according to this invention there isprovided a silver halide color photographic material containing abispyrazolone coupler which is the reaction product of a3-ureido-5-pyrazolone type magenta coupler and a compound having analdehyde group.

DETAILED DESCRIPTION OF THE INVENTION According to one embodiment ofthis invention, the color photographic material comprises a supporthaving coated thereon a silver halide emulsion layer containing anon-dilfusible bis-3-ureido-5-pyrazolone represented by general formulaI wherein R represents an alkyl group having 1 to 19, preferably, 1 to 7carbon atoms (e.g., a methyl, ethyl, isopropyl, tert-butyl, amyl, hexyl,octyl, decyl, dodecyl, pentadecyl, cyclohexyl, terpenyl or norbornylgroup), a (mono)aralkyl group having 7 to 9 carbon atoms (e.g., a benzylor cinnamyl group) or an aryl group (e.g., a phenyl or naphthyl group),where the aforesaid groups each may have one or more substituents suchas a halogen atom, a nitro group, a hydroxyl group, a carboxy group, anamino group (e.g., amino, N-alkylamino, N,N- dialkylamino, anilino orN-alkylanilino group, the alkyl group having 1 to 8, preferably, 1 to 4carbon atoms), a carboxyester group (e.g., an alkoxycarbonyl grouphaving 1 to 8, preferably, 1 to 4 carbon atoms in the alkyl moiety or anaryloxycarbonyl group wherein the aryl moiety is a phenyl or naphthylgroup which may be substituted with an alkyl group having 1 to 4 carbonatoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom), anamide group (e.g., an acetamide, butylamide, ethylsulfonamide orN-methylbenzamide group), a carbamyl group (e.g., a carbamyl orN,N-diethylcarbamyl group), a sulfamyl group (e.g., an N-propylsulfamyl, N,N-diethylsulfamyl or N-tolylsulfamyl group), analkoxyl group having 1 to 12, preferably, -1 to 4 carbon atoms (e.g., amethoxy or dodecyloxy group), an aryloxy group (e.g., a phenoxy ortolyloxy gro p), a sulfo group, a sulfonyl group (e.g., anethylsulfonyl, phenylsulfonyl or phenoxysulfonyl group), and the like.

R represents an alkyl group having 1 to 22 carbon atoms (e.g., a methyl,ethyl, propyl, isopropyl, butyl, tert-butyl, amyl, hexyl, octyl, decyl,dodecyl, pentadecyl, octadecyl or docosanyl groups) or an aryl group(e.g., a phenyl or naphthyl which may be substituted with halogen,cyano, nitro, alkyl having 1 to 18, preferably, 1 to 5 carbon atoms,alkoxy having 1 to 18, preferably 1 to 5 carbon atoms, aryl such asphenyl, tolyl and the like, aryloXy such as phenoxy and the like,carbamoyl, sulfamoyl, sulfonamido, acyl, acylamino such as acetamido,u-(2,4-di-tert-amylphenoxy)butylamido and the like or sulfo, forexample, a phenyl, 2-cl1loropheny1, Z-methoxyphenyl, 2-ethoxyphenyl,4-methylphenyl, 2,4,6-trichl0rophenyl, 2,5-dichlorophenyl,2,4-dichloro-G-methylphenyl, 2,4-dimethyl-G-chlorophenyl,2,6-dichl0r0-4-methylphenyl, 2,6-dichloro-4-methoxyphenyl,3,5-dibromophenyl, 2,6-dichloro-4-acylaminophenyl,2,6-diethyl-3-acylaminophenyl, 4-sulfophenyl, naphthyl or2-chloronaphthyl group).

R represents an alkyl group having 1 to 32 (e.g., a methyl, ethyl,propyl, isopropyl, butyl, tert-butyl, amyl, hexyl, octyl, decyl,dodecyl, pentadecyl, octadecyl, docosanyl, allyl, heptadecenyl,cyclohexyl, terpenyl or norbornyl group), an aralkyl group having 7 to9' carbon atoms (e.g., a benzyl or cinnamyl group) or an aryl group(e.g., a phenyl or naphthyl group), where each of these groups may havethe substituent as described for R The term non-diffusible is oneusually applied to Coupler (3) color couplers in the field of colorphotography and means that the coupler does not substantially move inthe colloid layer of a photographic material in the presence NHG ONH-CCHof an aqueous alkaline processing solution. 1

The bis-3-ureido-5-pyrazolone couplers represented by t-O5Hu- OCHCONH-general formula I in which R is a phenyl group having N a halogen atomor an alkoxyl group having 1 to 5 car- H113!) bon atoms as substituentsat least one ortho position (t) 01 1 thereof are especially preferred.

It is preferred that in the coupler of general formula I at least one ofR R and R has a ballast group which (I)CH3 2 makes the couplernon-diffusible. As is known in the art, 'ballast groups are hydrophobicgroups usually containmg 8 to 32 carbon atoms. Various kinds of ballastgroups are well known and may suitably be employed.

Examples of the ballast groups are described in US. Pats. 2,600,788;2,865,751; 3,337,344 and 3,418,129 and cwPler (4) Japanese PatentPublications 27,563/64 and 19,035/70.

Typical examples are represented by the following for- NHCONH C CH-NHOO-CHO LII .Jn R1 (0) COR;

-NHCOCHCH2N a, COR CHCH=CH '--S OZN R" Coupler (5) -CO0Rn a)@NnooNH-o-e1er crr cm)mon, wherein R R R R R R and R each represents11*]! :0 an alkyl group; R R and R each represents a hydrogen atom or analkyl group; and n is an integer of 1 to 7 5. Generally, any alkyl groupfor the groups R; to R de- 91 scribed above contains from 1 to 18 carbonatoms.

Among the bis3-ureido-5-pyrazolone couplers represented by the generalformula I, the couplers of the formula in which R represents a phenylgroup having a 1 2 ballast group as described above are particularlypre- Coupler (6) ferred.

Specific examples of the bis-3-ureido-5-pyrazolone counn nC ONE Coupler17) NH 0 o bnoQ-oumo Coupler l 8) Hum The bis-3-ureido-5-pyrazolone usedin this invention can be prepared by condensing 3-ureido-5-pyrazolonewith a compound having an aldehyde group. This condensation ispreferably carried out using 2 to 2.2 moles of 3-ureido- 5-pyrazoloneper 1 mole of the aldehyde in an inert organic solvent such as ethylalcohol, ethyl acetate, etc. at a temperature in the range of from to 80C., usually at atmospheric pressure, for a period of from 1 to 6 hours.In the above condensation, the concentration of the reactants in thesolvent is generally not critical.

The compund having an aldehyde group used in the above condensation canbe represented by the formula wherein R is as defined above for thecompound of the formula (I). Preferred examples of the aldehydes arebenzaldehyde or substituted benzaldehydes where the substituents are aspreviously defined. Representative examples of the aldehyde includeacetaldehyde, propionaldehyde, butylaldehyde, iso-butylaldehyde,pivalylaldehyde, heptaldehyde, laurin aldehyde, stearinaldehyde,succindialdehyde, crotonaldehyde, benzaldehyde, o-chlorobenzaldehyde,m-chlorobenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde,p-nitrobenzaldehyde, p-hydroxybenzaldehyd,e o-tolualdehyde,cinnamaldehyde and anaphthaldehyde. The starting material,B-ureido-S-pyrazolone, can be prepared by the methods described in US.Pat. 3,558,319 and German OLS 2,156,913 and 2,160,166.

Specific examples of preparing the bis-3-ureido-5-pyrazolones used as amagenta coupler in this invention are illustrated below.

Production of 4,4'-p-nitrobenzylidene-bis-1-(2,6-dichlor0 4methoxyphenyl) 3 [3-{a-(2,4-di-tert-amylphenoxy)butylamido}phenylureido] -5-pyrazolone (Coupler 142 g. of1-(2,6-dichloro-4-methoxvphenyl)-3-[3-{u- (2,4 di-tertamylphenoxy)butylamido}phenylureid0]-5- pyrazolone and 15- g. ofp-nitrobenzaldehyde were dissolved in 1500 ml. of ethyl acetate. Afterrefluxing for 2 hours at atmospheric pressure, the product was allowedto stand at room temperature and the precipitates formed were recoveredby filtration and reccrystallized from ethyl acetate to give4,4'-p-nitrobenzylidene-bis-1-(2,6-dichloro- 4-methoxyphenyl) 3 [3 a-(2,4-di-tert-amylphenoxy) butylamido}phenylureido]-5-pyrazolone meltingat 188- 190 C.

Production of 4,4-p-chlorobenzylidene-bis 1(2,6-dichloro-4-methoxyphenyl)-3-[3-{a (2,4di-tert-amylphenoxy)butylarnido}phenylureido] 5 pyrazolone (Coupler 142g. of 1-(2,6-dichloro-4-methoxyphenyl) 3 [3-{a- (2,4 di-tertamylphenoxy)butylamido}phenylureido]-5- pyrazolone and 14 g. ofp-chlorobenzaldehyde were dissolved in 1500 ml. of ethyl acetate. Afterrefluxing for 3 hours at atmospheric pressure, the product was distilledto remove ethyl acetate and the residue was dissolved in 3 liters ofacetonitrile. When the solution was allowed to stand at roomtemperature, crystals, precipitated. The crystals were recovered byfiltration under reduced pressure and washed with acetonitrile to give4,4-p-chlorobenzylidene-bis1-(2,6-dichloro 4 methoxyphenyl)-3-[3- {a(2,4 -di tert-amylphenoxy) butylamido}phenylureido]-5-pyrazolone meltingat -172 C.

Production of 4,4-p-nitr0benZylidene-bis-1-(2,6-di-chlo-'ro-4-methoxyphenyl) 3[3-(2,4-di-tert-amylphenoxyacetamido)phenylureido]-5-pyrazolone (Coupler(13)):

50 g. of1-(2,6-dichloro-4-methoxyphenyl)-3[3-(2,4-ditert-amylphenoxyacetamido)phenylureido]5 pyrazolone and 5.5 g. of p-nitrobenzaldehyde were dissolved in 1000ml. of ethanol. After refluxing the system for 4 hours at atmosphericpressure, ethanol was distilled off and the,

solution was allowed to stand at room temperature, crystalsprecipitated. The crystals were recovered by filtration and washed withmethanol to give 4,4-p-nitrobenzylidenebise1-(2,6-dichloro 4methoxyphenyl)-3-[3-(2,4-di-tertamylphenoxyacetarnido)phenylureido]--pyrazolone.

According to this invention the bis-3-ureido-5-pyrazolone magentacouplers may be used individually or as a mixture of two or more of suchcouplers, or may be used together with other known 2-equivalent or4-equivalent magenta couplers. These well-known couplers are sometimescalled colorless couplers, colored couplers or DIR couplers, andspecific examples thereof are described in U.S. Pats. 2,455,170;2,600,788; 2,908,573; 3,062,653; 3,148,062; 3,227,551; 3,227,554;3,418,129; 3,516,831; 3,519,429; 3,558,319 and 3,617,291. In a mixedcoupler system, the use of more than about 5 mol percent of abis-B-ureido-S-pyrazolone of this invention based on the total magentacouplers is effective.

The color coupler of this invention is incorporated in a hydrophiliccolloid constituting a photographic material according to a knownmanner. For instance, it can be dispersed in the hydrophilic colloid asa solution thereof in a high boiling organic solvent such as dibutylphthalate and tricresyl phosphate as described in U.S. Pat. 2,322,027,etc., and/or a low boiling organic solvent such as ethyl acetate andtetrahydrofuran as described in US. Pats. 2,801,170; 2,801,171 and2,946,360.

Any known hydrophilic colloid can be used for the silver halide emulsionlayers in this invention. Preferred examples of the hydrophilic colloidare gelatin, gelatin derivatives such as acylated gelatin as describedin U.S. Pats. 2,523,753 and 2,691,582, and graft gelatin as described inU.S. Pat. 2,831,767 and British Patent 1,211,- 039, albumin, gum arabic,agar agar, cellulose derivatives (such as alkyl esters of carboxymethylcellulose, hydroxyethyl cellulose, carboxymethylhydroxyethyl cellulose,etc.), and synthetic resins (such as polyvinyl alcohol, polyvinylpyrrolidone, etc.). These hydrophilic colloids are further preferablyused as binders for layers of the photosensitive materials other thanthe silver halide emulsion layers (for instance, protective layers,filter layers, intermediate layers, antihalation layers, subbing layersand backing layers).

The hydrophilic colloids used for the various layers of the photographicmaterials of this invention are preferably hardened by a hardening agentsuch as a 1,4-dioxane or aziridine type hardening agent, an iso-oxazoletype hardening agent, an active halogen type hardening agent, an activevinyl type hardening agent, etc. Typical examples'of such hardeningagents are described in U.S. Pats. 3,232,- 764; 3,288,775; 2,732,303;3,635,718; 3,232,763; 2,732,- 316; 2,586,168; 3,103,437; 3,017,280;2,983,611; 2,725,- 294; 2,725,295; 3,100,704; 3,091,537; 3,321,313 and3,543,292 and British Pats. 974,723; 1,167,207 and 994,869. In thepresent invention, all silver halide emulsions as are used in the fieldof photography, such as a silver bromide emulsion, a silver iodideemulsion, a silver chloroiodobromide emulsion, a silver chlorobromideemulsion and a silver chloride emulsion can be used. Also, the socalledconverted halide type silver halide grains as disclosed in U.S. Pat.3,622,318 and British Pat. 635,841 may be profitably used in thisinvention. A preferred average grain size for the silver halide is fromabout 0.05 to about 1.5 microns. The weight ratio of silver halide tobinder most suitably ranges from about 0.2 to about 20 (silverhalide/binder), preferably about 0.3 to about 5 in the layer. Generally,the ratio of a silver halide/a couple of the present invention is fromabout 1 to 40, preferably 2 to 20. These values are not limitative, butprovide a most superior element.

The silver halide emulsions of this invention can be chemicallysensitized by active gelatin or a sulfur compound according to theprocess described in U.S. Pats.

1,574,944; 1,623,499 and 2,410,689. They can also be sensitized by anoble metal salt such as a palladium or a gold salt as described in U.S.Pats. 2,448,060; 2,399,083 and 2,642,361. Furthermore, they can besensitized by a reducing agent such as a stannous salt as described inU.S. Pat. 2,487,850, or sensitized by a polyalkylene derivative. Theycan also be spectra'lly sensitized by a cyanine or merocyanine dye suchas described in U.S. Pats. 2,519,001; 2,666,761; 2,734,900; 2,739,964and 3,481,742. The silver halide emulsion may further contain astabilizer such as a mercury compound, mercaptotetrazole, thiazole,azaindene, etc.; a plasticizer such as glycerin, a latex, etc.; and acoating aid such as saponin, polyethylene glycol monolauryl ether, etc.Furthermore, the silver halide emulsion may contain an antistatic agent,an ultraviolet absorbent, a fluorescent brightening agent, a dye, andthe like.

The silver halide emulsion containing the bis-3-ureido- S-pyrazolonecoupler of this invention is most profitably used as the green-sensitivephotosensitive layer in a multicolor type color photographic material.In this case, the disposition order of the photosensitive emulsionlayers may be, from the support side, a red-sensitive layer, agreen-sensitive layer, and a blue-sensitive layer, or, alternatively ablue-sensitive layer, a red-sensitive layer and a green-sensitive layer.The photographic material may also have, besides those photosensitivelayers, an antihalation layer, intermediate layers, a filter layer, anda protective layer.

Preferred examples of the support on which the silver halidephotosensitive emulsion layers are carried are cellulose ester filmssuch as cellulose nitrate films, cellulose acetate films, etc.;polyester films such as polyethylene terephthalate films, etc.;polyvinyl chloride films; polystyrene films; polycarbonate films,baryta-coated papers; resin-coated papers; and the like.

The color photographic material of this invention is imagewise exposedaccording to an ordinary manner and then processed by standard colorprocessing procedures. The main processing steps are color development,bleach and fix. A washing step may be applied, if desired, between thesesteps. After fixing, the color photographic material is washed and driedbut it is desirable to process it in a fix bath before drying.

As is known to those skilled in the art, photographic processingtemperatures typically range from about 20 C. or less to 60 C. orhigher. Temperatures of about 30 C. or higher are suitable for highspeed processing procedures.

A useful color developer is an alkaline aqueous solution containing acolor developing agent. As the color developing agent all known aromaticprimary amine dye-forming developing agents can be used. For instance,there are phenylenediamines such as N,N diethyl-p-phenylenediamine, Nethyl-N-hydroxyethyl-pphenylenediamine, N- ethylN-hydroxyethyl-2-methyl-p-phenylenediamine, N- ethyl flN-methanesulfonamidoe'thyl-3-methyl-4-aminoaniline,N,N-Z-methyl-p-phenylenediamine, sulfates thereof, hydrochloridesthereof and sulfites thereof. See C. E. K. Mees and T. H. James, TheTheory of the Photographic Process, pages 294295 (The MacMillan Co.,1966), and U.S. Pats. 2,592,364 and 2,193,015. The color developer maycontain ordinary additives such as an alkali metal sulfite, a carbonate,a bisulfite, a bromide, an iodide, benzyl alcohol, etc.

As the bleach solution, all known bleach solutions containing aferricyanide, a bichromate, etc., can be used. Also, all known fixsolutions containing sodium thiosulfate, potassium thiocyanide, etc.,may be used as the fix solution. Furthermore, the bleaching step and thefixing step may be conducted in one bath. Such a blix bath is describedin, e.g., U.S. Pat. 3,582,322. Typical bleach agents are discussed indetail in the Journal of the Society of Motion Picture and TelevisionEngineers 61,.667-701 and U.S. Pat. 3,189,452; typical fix agents inMason,

Photographic Processing Chemistry, pages 187-188, Focal Press (1966);and typical blix solutions in German Patents 866,605 and 966,410, inBritish Journal of Photography, pages 122-123 and 126 (1966) and in US.Pat. 3,582,322. These references also disclose generally usedproportions.

The feature of this invention lies in the point that the magenta coupleris a bis-compound having a ureido bond at the 3-position of thepyrazolone. Even if the photographic material of this inventioncontaining such a coupler is exposed to heat or moisture or is storedfor a long period of time it provides a stable color image giving lessfading. Also, the magenta coupler of this invention has the merit thatit does not cause insufficient coloring, which usually happens in thecase of using conventional bis-type magenta couplers. Furthermore, themagenta coupler of this invention has the effect of controlling theoccurrence of development fog. Moreover, in the photosensitive emulsionlayer containing the magenta coupler of this invention, changes insensitivity during storage are suppressed. This surprising effect isalso observed in the emulsion layer formed on or under the emulsionlayer containing the magenta coupler of this invention.

The invention will now be illustrated more in detail by the followingexamples.

EXAMPLE 1 60 g. of a coupler dispersion prepared by dispersing asensitizing dye having its sensitization maximum at about 545 m and thefollowing components by means of a homogenizer was added to 100 g. of asilver chlorobromide emulsion (bromine content: 50 m1. percent)containing 0.05 mol of silver and the mixture was coated on abaryta-coated paper (amount of coated silver was 6 10- mol/m3). SamplesA, B and C were thus produced.

A B C Coupler dispersion:

Coupler (3) g 100 Coupler (6) g 100 Comparison coupler A, g- 1000Dibutyl phthalate, g- 100 100 100 Ethyl acetate, g 200 200 200 10%aqueous gelatin solution, g 1, 000 1, 000 1, 000 5% aqueous solution ofsodium dodecylbenzenesulionate, g 50 50 50 Comparison coupler A:

N HC ONH- C-CH1 CzHi il E} N tert-C H -O HOONH- \N/ I O CH:

Each of the samples Was subjected to a staged exposure of 1000 lux for/2 seconds through a green filter transmitting light of 500-600 mg and asilver wedge and then subjected to the following processings.

The formulations of the processing solutions used in the aboveprocessings were as follows:

Color developer:

Sodium metaborate g 25 5 Sodium sulfite g 2 Hydroxylamine (sulfate) g 2Potassium bromide g 0.5 6-Nitrobenzimidazole (nitrate) g 0.02 Sodiumhydroxide g 4 l0 Benzyl alcohol ml 15.8 Diethylene glycol ml 20 N-EthylN ,8 (methanesulfonamidoethyl)- p phenylenediamine g 8 Water to make ml1000 Blix solution:

Iron salt of ethylenediamine tetraacetic acid g 45 Ammonium thiocyanateg 10 Sodium sulfite g 10 Ammonium thiocyanate (60% aqueous solution) m1100 Ethylenediamine tetraacetic acid tetrasodium salt g 5 Water to makeml 1000 Stabilization bath:

Tartaric acid g 10; Zinc sulfate g 10 Sodium metaborate g 20 Water tomake ml 1000 After measuring the reflection density of the magenta dyeimage thus formed, each sample was stored for 14 days of 60 C. and 70%relative humidity to conduct a fading test, and then the reflectiondensity of the color image was measured again. The dye remaining rate(percentage) of the portions of the sample having image densities of 0.5and 1.5 before the fading test was calculated by the following equation,and the results are shown in Table 1.

Dye remaining rate (percent) X 100 wherein A=dye density after thefading test-fog density after the fading test; B=dye density before thefading test-fog density before the fading test.

Dye remaining rate (percent) Initial Initial Sample density 0.5 density1.5 86 90 88 92 45 60 As is clear from the above results, samples A andB containing a bis-3-ureido-5-pyrazolone magenta coupler according tothis invention have stable magenta dye images showing less fading andthis tendency Was particularly remarkable at the low-density portion. Onthe other hand, in the case of using comparison coupler A (this couplercorresponds to a mono-type, i.e., mono-3- ureido-5-pyrazolone type, ofCoupler (3) and Coupler (6)), the color image formed showed greatfading.

EXAMPLE 2 coupler. A gelatin intermediate layer was coated on theblue-sensitive layer, and, further, a coating composition containing asilver chlorobromide emulsion containing 30 mol percent bromine andspectrally sensitized so that the silver halide emulsion had itssensitization maximum at about 685 m and a coupler dispersion preparedby dispersing a cyan coupler,1-hydroxy-4-chloro-N-hexadecyl-'N-(2-cyanoethyl)-2-naphthamide, in amixture of dibutyl phthalate and ethyl acetate was coated on theintermediate layer to give a red-sensitive emulsion layer containing 7.410 mol/m. of a silver halide and 1.7 10 mol/m. of the coupler. A gelatinintermediate layer was coated on the red-sensitive emulsion layer, and,further, a coating composition consisting of 100 g. of a silverchlorobromide emulsion (bromide content: 35 mol percent containing 0.06mol of silver and spectrally sensitized so that the emulsion had thesensitization maximum at about 555 m and 250 g. of a coupler dispersionprepared by dispersing the following components by means of ahomogenizer was coated on the intermediate layer to give agreen-sensitive emulsion layer containing 2x10 mol/m? of a silver halideand 1.5 10 mol/m. of the coupler. Finally, a gelatin protective layerwas coated on the green-sensitive layer. Thus, samples D, E, F and Gwere prepared.

D E F G Coupler dispersion:

Coupler (2), g 30 Coupler (6), g 30 Coupler (11), g 30 Known coupler E,g 70 70 70 100 Dubutyl phthalate, g. 50 50 50 50 Ethyl acetate, g 200200 200 200 10% aqueous gelatin soln., g 1, 000 1, 000 1, 000 1, 000

% aqueous solution of sodium dodecylbenzene sulfonate, g 100 100 100 100Each of the samples thus prepared was exposed as in Example 1 andsubjected to the following processings.

Temperature, C. Time Processing:

Pre-processing bath.. 27 sec. Washing 27 15 sec. Color development. 27 5min. sec. Washing 27 15 see. Blix 27 4 min. Washing 27 2 min.Stabilization 27 10 sec.

The formulations of the processing solutions used in the aboveprocessings were as follows: Pre-processing bath:

14 Blix solution:

Sodium iron (III) ethylenediamine tetraacetic After measuring thetransmission density of the magenta dye images thus formed, each samplewas stored for 30 days at 50 C. and 70% relative humidity to conduct afading test, and then the transmission density of the dye images wasmeasured again. The dye remaining rate (percentage) at portions havingimage densities of 0.5 and 20 before the fading test are shown in Table2.

TABLE 2 Dye remain rate (percent) Initial Initial Fog density densitydensity 0.5 20

From the above results, it was clear that the photographic material ofthis invention containing a bis-3- ureido-S-pyrazolone shows aneffective fading prevention effect in the color image, even if thecontent thereof was about 15 mol percent of the total couplers, and alsoin the photographic materials the formation of magenta development fogWas suppressed.

EXAMPLE 3 On a paper support having coated on both surfaces polyethylenecontaining titanium dioxide, a coating composition containing a silverchlorobromide emulsion containing 85 mol percent bromine and a couplerdispersion prepared by dispersing a yellow coupler, oc(4-methoxybenzoyl)3 [ot-(2,4-di-tert-amylphenoxybutylamido)]- 6-chloro-acetanilide, in amixture of dibutyl phthalate and ethyl acetate was coated to give ablue-sensitive emulsion layer containing 9X10- mol/m. of silver and 7X10- mol/m. of the coupler, and then an intermediate layer of gelatin wascoated on the blue-sensitive layer. A coating composition consisting ofg. of a silver chlorobromide emulsion containing 30 mol percent bromideand 0.07 mol of silver and 100 g. of a coupler dispersion prepared bydispersing a sensitizing dye having its sensitization maximum at about545 m and the following components by means of a homogenizer Was coatedon the intermediate layer (amount of coated silver was 1 10 mol/m Thus,samples H, I, J, K, and L were prepared.

Coupler dispersion:

Coupler (3), g Coupler (9) g-.. Coupler (15), g. Coupler (16), g-

1 5 Coupler C:

o ONH-C-CH: CzHs tort-05H" O HCONH- \N/ 'a protective layer of gelatinwas coated on the emulsion layer. Thus, Samples H, I, J, K and L wereprepared.

Directly after the production of the samples or after storing them for 3days at 40 C. and 80% relative humidity, each of the samples was wedgeexposed to the light of 1000 lux for 1 second through a filtertransmitting light of 500-6001;. and a filter transmitting light havingwave lengths longer than 600 1., and then processed as in Example 1.

The red sensitivity and the green sensitivity were measured for eachsample and the change of sensitivity upon storage under thehigh-temperature and high-humidity conditions (for 3 days at 40 C. and80% relative humidity) was measured, the results of which are shown inTable 3. In Table 3, -0.15 shows that the sensitivity of the storedsample was reduced as compared with that of the fresh sample by 0.15(logarithmic units). Also, the fog density of the stored sample wasmeasured and a fading test on the sample as in Example I was conducted,the results also being shown in Table 3.

As is clear from Table 3, by using the bis-type magenta coupler of thisinvention in an amount of about 15 mol percent of the total magentacouplers, the stability of the magenta color images was improved, theformation of magenta development fog when the photographic material waspreserved under high-temperature and highhumidity conditions wassuppressed, and, further the change in sensitivities in thegreen-sensitive layer and the red-sensitive layer was lessened.

From the specific examples described above, it will be understood thatexcellent characteristics were obtained using thebis-3-ureido-5-pyrazolones according to this invention.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:

1. A silver halide color photographic material comprising a supporthaving thereon an emulsion layer containing thebis-3-ureido-5-pyrazolone represented by the general formula wherein Rrepresents an alkyl group, an aralkyl group or an aryl group, Rrepresents an alkyl group or an aryl group; and R represents an alkylgroup, an aralkyl group, or an aryl group.

2. The silver halide color photographic material as set forth in Claim 1in which at least one of said groups R R and R has a ballast group.

References Cited UNITED STATES PATENTS 2,294,909 9/ 1942 Jennings 96-1002,618,641 11/1952 Weissberger et a1 96-100 3,393,071 7/1968 Monbaliu etal 96-100 3,468,666 9/1969 Shiba et a1 96-100 3,558,319 1/1971 Hamaokaet al 96-100 I. TRAVIS BROWN, Primary Examiner U.S. Cl. X.R.

